JP2023021183A - Thermoplastic resin composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in mechanical properties and colorability, and enables molding by re-melting, and a method for producing the same.

SOLUTION: There is provided a thermoplastic resin composition in which a sea structural part of a thermoplastic resin composition having a sea-island structure is composed of a thermoplastic resin, an island structure part is composed of a thermoplastic elastomer and/or a rubber material crosslinked by a siloxane bond, a gel fraction (according to JIS K 6769:2004) of the island structure part is 90% or more, and a free radical generated by a reaction initiator contained in the thermoplastic resin composition has radical activity inactivated by a reaction terminator contained in the thermoplastic resin composition in a ratio of a mol number of 100% or more with respect to a mol number of the reactive initiator.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which has excellent mechanical properties and colorability and which can be molded by remelting, and a method for producing the same.

Thermoplastic elastomer compositions that can be molded by extrusion molding or injection molding are used for automotive parts such as weather strips, roof moldings, and mudguards, construction materials such as waterproof materials and joint materials, and industrial materials such as hoses. ing.
Thermoplastic elastomer compositions include those dynamically crosslinked by blending polypropylene (PP), ethylene propylene diene rubber (EPDM), oil, crosslinking agent, etc. In the case of complete crosslinking, a phenolic crosslinking agent is used as the crosslinking agent is used, and in the case of partial cross-linking, a peroxide cross-linking agent is used as a cross-linking agent (Patent Documents 1 and 2).
In addition, a masterbatch made from polyethylene (PE), a silane coupling agent, and a peroxide (reaction initiator) is mixed with a catalyst masterbatch such as tin, and molded. There is a silanol-crosslinked resin crosslinked with, etc. (Patent Document 3).

JP-A-5-170930 Japanese Patent Publication No. 58-46138 JP-A-10-245424

However, a thermoplastic elastomer composition (TPV) dynamically crosslinked using a phenol-based cross-linking agent is excellent in mechanical properties such as compression set due to complete cross-linking, but an orange color due to phenol appears in the molded product. There is a problem that the coloring freedom is low. On the other hand, a TPV dynamically crosslinked using a peroxide crosslinking agent has a problem of poor mechanical properties due to partial crosslinking, although the peroxide crosslinking agent itself is colorless and transparent and has a high degree of freedom in coloring.
Moreover, once crosslinked, silanol crosslinked resins cannot be remelted and cannot be remolded, resulting in a problem of low molding flexibility.

The present invention has been made in view of the above points, and an object of the present invention is to provide a thermoplastic resin composition which is excellent in mechanical properties and colorability and which can be molded by remelting, and a method for producing the same.

The invention of claim 1 is a thermoplastic resin composition having a sea-island structure, wherein the sea-structure part of the sea-island structure is made of a thermoplastic resin, and the island-structure part of the sea-island structure is crosslinked by a siloxane bond. is composed of a thermoplastic elastomer and/or a rubber material, the gel fraction (JIS K6769: 2004 compliant) of the island structure portion is 90% or more, and the reaction initiator contained in the thermoplastic resin composition The generated free radicals are deactivated in radical activity by the reaction terminator contained in the thermoplastic resin composition at a molar ratio of 100% or more with respect to the molar number of the reaction initiator.

The invention according to claim 2 is the thermoplastic elastomer and/or rubber material according to claim 1, wherein the main chain and the side chain are a thermoplastic elastomer having saturated bonds, and the thermoplastic resin comprises a main chain and a side chain. is a thermoplastic resin composed of saturated bonds.

The invention of claim 3 is the thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition is used as a joint material for building materials, a water stop material for building materials, an interior material for vehicles, an exterior material for vehicles, and an industrial hose material. It is characterized by

In the invention of claim 4, a thermoplastic elastomer and/or rubber material having an alkoxysilyl group, in which an alkoxysilyl group is grafted to a thermoplastic elastomer and/or rubber material, and a reaction terminator are mixed in a kneader. The reaction terminator deactivates the free radicals derived from the reaction initiator blended to produce the thermoplastic elastomer and/or rubber material having the alkoxysilyl group by kneading in a molten state, and the radical activity is deactivated. A reaction termination step of producing a thermoplastic elastomer and/or rubber material having activated alkoxysilyl groups, a thermoplastic elastomer and/or rubber material having the alkoxysilyl groups whose radical activity has been deactivated, and a thermoplastic resin. , a kneading step of kneading to a molten state in a kneader, adding a water component to the kneader, and producing a thermoplastic elastomer and / or rubber material having an alkoxysilyl group whose radical activity has been deactivated in the kneader. an alkoxysilyl group and the water component are hydrolyzed to form a silanol group, and then the silanol groups are subjected to a condensation reaction to form a siloxane bond; The ratio of the number of moles of the reaction terminator added to the number of moles of the reaction initiator is 100% or more, and the thermoplastic resin composition obtained by the dynamic crosslinking step has a sea-island structure. It relates to a method for producing a thermoplastic resin composition.

The invention of claim 5 is based on claim 4, wherein in the dynamic crosslinking step, the alkoxysilyl groups of the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated pass through the silanol groups. , when the siloxane bond is formed, the viscosity of the thermoplastic elastomer and/or rubber material having an alkoxysilyl group whose radical activity is deactivated becomes higher than the viscosity of the thermoplastic resin, and the radical activity is deactivated. The thermoplastic elastomer and/or rubber material having active alkoxysilyl groups undergoes a phase transition to the island structure portion of the sea-island structure, and the thermoplastic resin undergoes a phase transition to the sea structure portion of the sea-island structure. .

The invention according to claim 6 is characterized in that, in claim 4 or 5, the gel fraction (in accordance with JIS K6769:2004) of the island structure portion of the sea-island structure is 90% or more.

The invention of claim 7 is the thermoplastic elastomer and/or rubber material according to any one of claims 4 to 6, in order to produce the thermoplastic elastomer and/or rubber material having the alkoxysilyl group, a grafting step of adding a silane coupling agent and a reaction initiator and kneading them into a molten state in the kneader to graft the silane coupling agent to the thermoplastic elastomer and/or rubber material; The grafting step, the reaction termination step, the kneading step, and the dynamic cross-linking step are performed continuously in the kneader.

The invention of claim 8 is characterized in that, in any one of claims 4 to 7, the sea structure portion of the sea-island structure is made of the thermoplastic resin and is remeltable.

The invention according to claim 9 is the colorant according to any one of claims 4 to 8, wherein 0.01 part by weight of the colorant is blended with 100 parts by weight of the thermoplastic elastomer and/or the rubber material. A color difference value of ΔE*ab (based on JIS Z8781-4:2013) due to coloring of the thermoplastic resin composition is 1.5 or more.

The invention of claim 10 is characterized in that, in any one of claims 4 to 9, the thermoplastic resin is a crystalline thermoplastic resin.

The invention of claim 11 is the thermoplastic elastomer and/or rubber material according to any one of claims 4 to 10, wherein the main chain and the side chain are a thermoplastic elastomer composed of saturated bonds, and the thermoplastic resin is characterized by being a thermoplastic resin in which the main chain and side chains are composed of saturated bonds.

The invention according to claim 12 is characterized in that, in claim 11, the thermoplastic resin in which the main chain and the side chains are composed of saturated bonds is an olefin resin.

A thirteenth aspect of the invention is characterized in that, in the twelfth aspect, the olefin-based resin is a polypropylene-based resin.

The invention of claim 14 is characterized in that, in the invention of claim 12 or 13, the thermoplastic elastomer in which the main chain and side chains are composed of saturated bonds is a polyethylene/α-olefin copolymer.

The invention of claim 15 is the color difference value after weather deterioration of the thermoplastic resin composition according to any one of claims 12 to 14: ΔE*ab (based on JIS Z8781-4:2013) is 0 to 3 It is characterized by

The invention of claim 16 is the thermoplastic resin composition according to any one of claims 4 to 15, wherein the thermoplastic resin composition is a It is characterized by being used as a hose material.

According to the inventions of claims 1 and 3, the sea structure portion of the sea-island structure is made of a thermoplastic resin, and the island structure portion of the sea-island structure is made of a thermoplastic elastomer and/or a rubber material crosslinked by siloxane bonds. The gel fraction (JIS K6769: 2004 compliant) of the island structure portion is 90% or more, and the free radicals generated by the reaction initiator contained in the thermoplastic resin composition are activated by the reaction terminator. is deactivated, mechanical properties and colorability are good, it is possible to re-melt and re-mold, and there is little deterioration in physical properties, and a thermoplastic resin composition with a high degree of molding freedom is obtained. be done.

According to the invention of claims 2 and 3, a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds and a thermoplastic resin whose main chain and side chains are composed of saturated bonds are used as raw materials, and a silane coupling agent is used. Because dynamic cross-linking is carried out in the process, the thermoplastic resin composition has excellent mechanical properties and colorability, can be re-melted and re-molded, has a high degree of freedom in molding, and is resistant to weather deterioration. can get.

According to the invention of claims 4 to 16, dynamic cross-linking is performed using a silane coupling agent, and further, the free radicals generated by the reaction initiator have their radical activity deactivated by the reaction terminator. A thermoplastic resin composition which has good mechanical properties and colorability, can be remelted and remolded, and has a high degree of freedom in molding can be obtained.

According to the invention of claims 12 to 16, a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds and a thermoplastic resin whose main chain and side chains are composed of saturated bonds are used as raw materials, and a silane coupling agent is used. Because dynamic cross-linking is carried out in the process, the thermoplastic resin composition has excellent mechanical properties and colorability, can be re-melted and re-molded, has a high degree of freedom in molding, and is resistant to weather deterioration. can get.

This is the reaction behavior when an alkoxysilyl group changes to a siloxane bond via a silanol group. 1 is a schematic view of a kneader that continuously performs a grafting step, a reaction termination step, a kneading step, and a dynamic cross-linking step; FIG. 1 is a table showing formulations and measurement results of physical properties of examples and comparative examples. 4 is a table showing ΔE*ab in terms of NBS units and color difference.

Embodiments of the thermoplastic composition and the method for producing the same of the present invention are described below.
The thermoplastic resin composition of the present invention is a thermoplastic composition having a sea-island structure, wherein the sea structure part of the sea-island structure is made of a thermoplastic resin, and the island structure part of the sea-island structure is formed by siloxane bonding. It is composed of a crosslinked thermoplastic elastomer and/or rubber material, and the gel fraction (JIS K6769: 2004 compliant) of the island structure portion is 90% or more, and the reaction initiator contained in the thermoplastic resin composition The free radicals generated by the agent are deactivated by the reaction terminator contained in the thermoplastic resin composition at a molar ratio of 100% or more with respect to the molar number of the reaction initiator. .

In addition, the thermoplastic elastomer and/or rubber material in the thermoplastic composition of the present invention is a thermoplastic elastomer whose main chain and side chains are saturated bonds, and the thermoplastic resin has a saturated main chain and side chains. It is preferably a thermoplastic resin composed of bonds.

In the thermoplastic composition of the present invention, the sea structure part of the sea-island structure is composed of a thermoplastic resin, and the island structure part of the sea-island structure is composed of a thermoplastic elastomer and/or a rubber material crosslinked by siloxane bonds, The gel fraction (JIS K6769: 2004 compliant) of the island structure portion is 90% or more, and the free radicals generated by the reaction initiator contained in the thermoplastic resin composition lose their radical activity by the reaction terminator. Because it is activated, it has good mechanical properties and colorability, can be remelted and remolded, and has a high degree of freedom in molding. It is suitable as an interior material, an exterior material for vehicles, and an industrial hose material.

The method for producing the thermoplastic resin composition has a reaction termination step, a kneading step, and a dynamic cross-linking step.
In the reaction stopping step of the present invention, when the grafting step described later is performed, after the grafting step and before the kneading step, when the grafting step is not performed, before the kneading step. By the time, the reaction terminator is added to the kneader and kneaded in a molten state, and the free radicals derived from the reaction initiator blended for grafting the alkoxysilyl group to the thermoplastic elastomer and / or rubber material are removed as described above. Inactivate with a reaction terminator. If the reaction terminator is mixed into the kneader before the grafting step is completed, the amount of alkoxysilyl groups grafted onto the thermoplastic elastomer and/or rubber material is reduced, and the gel fraction of the island structure portion is reduced. cannot be made more than 90%. On the other hand, when the reaction terminator is blended after the thermoplastic resin is blended in the kneader (during the kneading step), the thermoplastic resin is decomposed by free radicals present in the kneader and has a low molecular weight, resulting in mechanical properties. may decrease.

Examples of the reaction terminator (radical scavenger) include compounds capable of scavenge radicals such as phenolic antioxidants and hindered amine light stabilizers, and can be used alone or in combination of two or more. Hindered amine light stabilizers are more preferable because they themselves are colorless and have excellent radical scavenging properties. When using phenolic antioxidants, there are grades in which the phenolic antioxidants themselves are colored, and even grades that are not colored may become colored during processing with a kneader, etc. Therefore, it is preferable to select a grade that does not discolor even when processed with a kneader or the like. If a colored grade or a grade that is colored during processing is used, it is preferable that the blending amount be such that it does not affect the coloring of the thermoplastic resin composition. The addition of the reaction terminator into the kneader may be carried out by either mixing raw materials as they are or as a masterbatch.

The amount of the reaction terminator compounded is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.
In addition, in order to effectively deactivate the free radicals generated by the reaction initiator, the ratio of the amount (number of moles) of the reaction terminator added to the amount (number of moles) of the added reaction initiator, that is, the [reaction terminator (number of moles)/reaction initiator (number of moles)×100] is preferably 100% or more, more preferably 100 to 200%.

The thermoplastic elastomer (TPE) used in the present invention is not limited. Hydrogenated styrene ethylene propylene styrene copolymer (SEPS), hydrogenated styrene ethylene butadiene copolymer (SEBS), etc.), thermoplastic olefin elastomer (TPO), polymerized thermoplastic polyolefin elastomer (R-TPO) , Thermoplastic vinyl chloride elastomer (TPVC), Thermoplastic polyurethane elastomer (TPU), Thermoplastic polyester elastomer (TPC), Thermoplastic polyamide elastomer (TPA), Thermoplastic polybutadiene elastomer, Thermoplastic fluorine elastomer ( TPF) and the like can be used singly or in combination of two or more.

The thermoplastic elastomer includes a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds. It is a thermoplastic elastomer that does not contain unsaturated bonds. Examples of thermoplastic elastomers in which the main chain and side chains are composed of saturated bonds include polymeric thermoplastic polyolefin elastomers (R-TPO), thermoplastic polyvinyl chloride elastomers (TPVC), thermoplastic fluorine elastomers (TPF), and the like. and can be used singly or in combination of two or more. In particular, polymerizable thermoplastic polyolefin elastomers are preferred, and specific examples include ethylene/α-olefin copolymer elastomers. The copolymer portion of the ethylene/α-olefin copolymer may be either a random copolymer or a block copolymer.

The rubber material used in the present invention is not limited, and examples include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), nitrile rubber (NBR), Ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylic rubber (ACM) and the like can be used singly or in combination of two or more. Among rubber materials, rubber materials that do not contain unsaturated bonds such as double bonds in the main chain are preferable. Can be used together.

In the present invention, either one of the thermoplastic elastomer and the rubber material is used alone, or both are used in combination.

and/ Alternatively, if a rubber material is to be made, the grafting step is performed prior to the quenching step.
In the grafting step, the thermoplastic elastomer and/or rubber material, a silane coupling agent, a reaction initiator, and appropriate additives are added and kneaded in a kneader to a molten state to obtain the A thermoplastic elastomer comprising a thermoplastic elastomer and/or a rubber material having alkoxysilyl groups is produced.

The silane coupling agent is preferably a silane coupling agent used as a cross-linking agent and having an alkoxysilyl group. Examples of the silane coupling agent having an alkoxysilyl group include alkoxysilyl compounds having a vinyl group, alkoxysilyl compounds having an epoxy group, alkoxysilyl compounds having an acrylic group or a methacrylic group, and the like. can do. In particular, alkoxysilyl compounds having a vinyl group are more preferable because they have good reactivity with thermoplastic elastomers and/or rubber materials and are inexpensive. Specific examples of alkoxysilyl compounds having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane. The amount of the silane coupling agent compounded is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

Examples of the reaction initiator include dialkyl peroxide-based, diacyl peroxide-based, and alkyl perester-based initiators, and they can be used singly or in combination of two or more. In particular, dialkyl peroxides are preferred from the viewpoint of reactivity with the thermoplastic resin composition and cost. oxy)hexyne-3,2,5-dimethyl-2,5-di(t-butylperoxy)hexane and the like. The amount of the reaction initiator compounded is preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

Furthermore, it is preferable to blend a silanol cross-linking accelerating catalyst. Examples of the silanol cross-linking accelerating catalyst include dibutyl tin, fatty acid amide, and the like, and they can be used singly or in combination of two or more. The amount of the silanol cross-linking acceleration catalyst to be blended is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

Appropriate additives include synthetic resin stabilizers such as light stabilizers and antioxidants, processing aids such as lubricants and release agents, softeners, coloring agents, fillers, conductive agents, and flame retardants. etc., and can be blended within a range that does not affect the properties of the thermoplastic resin composition. The silanol cross-linking acceleration catalyst and appropriate additives may be appropriately blended into the kneader in each step of the kneading step and the dynamic cross-linking step in addition to the grafting step. Appropriate additives may be blended into the kneader by any blending method, such as blending the raw materials as they are or blending them as a masterbatch.

Synthetic resin stabilizers such as light stabilizers and antioxidants include phenol-based antioxidants, hindered amine-based light stabilizers, and the like, and can be used singly or in combination of two or more. By adding a synthetic resin stabilizer, the stability (weather resistance, etc.) of the thermoplastic resin composition can be further enhanced. As the synthetic resin stabilizer, the same compound as the reaction terminator can be used. The blending amount of the synthetic resin stabilizer is preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

Examples of processing aids such as lubricants and release agents include metal soaps such as erucamide and calcium stearate, and they can be used singly or in combination of two or more. By blending the processing aid, it is possible to stabilize the ejection of the thermoplastic resin composition at the outlet of a kneader such as an extruder and prevent melt fracture. The amount of the processing aid compounded is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

Examples of the softening agent include paraffinic oils, olefinic oils, naphthenic oils, aromatic oils, and the like, and they can be used singly or in combination of two or more. Since naphthenic oils and aromatic oils themselves are colored pale yellow or the like, it is more preferable to use colorless paraffinic oils and olefinic oils. The blending amount of the softening agent can be appropriately adjusted according to the desired hardness, and is preferably 0 to 150 parts by weight based on 100 parts by weight of the thermoplastic elastomer and/or rubber material.

As the coloring agent, coloring materials such as pigments of various colors can be mentioned, and one kind or a combination of two or more kinds can be used for toning. The colorant may be directly added to the kneader, but it is preferable to use a masterbatch that is excellent in dispersibility and uniformity and free from scattering and staining of the kneader. The amount of the coloring agent to be blended is preferably 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material, although it depends on the desired color.

In the kneading step of the present invention, the thermoplastic elastomer and/or rubber material having an alkoxysilyl group whose radical activity has been deactivated, the thermoplastic resin, and appropriate additives are added in the kneader, and the mixture is melted. knead.

The thermoplastic resin (TP) blended in the kneading step may be either crystalline or amorphous, or both may be used in combination. Examples of crystalline thermoplastic resins include olefin resins (PO), polyacetal resins (POM), polyamide resins (PA), polyester resins (polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.), and the like. Examples of amorphous thermoplastic resins include polystyrene-based resins (PS), polycarbonate-based resins (PC), polyvinyl chloride-based resins (PVC), and the like. . The amount of the thermoplastic resin compounded is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight, per 100 parts by weight of the thermoplastic elastomer and/or rubber material.

The thermoplastic resin includes a thermoplastic resin in which the main chain and side chains are composed of saturated bonds. It is a thermoplastic resin that does not contain unsaturated bonds. Examples of the crystalline thermoplastic resin in which the main chain and side chains are saturated bonds include olefin resins, polyacetal resins, etc. The amorphous thermoplastic resin in which the main chain and side chains are saturated bonds include: Examples include polyvinyl chloride resins.

A crystalline thermoplastic resin is preferable as the thermoplastic resin to be blended in the kneading step. This is because, in the kneading step, the thermoplastic elastomer and/or rubber material having alkoxysilyl groups and the thermoplastic resin are in a molten state, and in the dynamic cross-linking step of the next step, the alkoxy alkoxy When a silyl group forms a siloxane bond, a crystalline thermoplastic resin with a definite melting point (Tm) produces a viscosity difference compared to an amorphous thermoplastic resin that does not have a definite melting point. This is because the phase transition is likely to occur.

When a crystalline thermoplastic resin whose main chain and side chains are composed of saturated bonds is used as the thermoplastic resin blended in the kneading step, the water component blended in the dynamic cross-linking step contacts the thermoplastic resin. However, the thermoplastic resin does not deteriorate such as by hydrolysis, and the main chain and side chains do not contain unsaturated bonds such as double bonds. . As the crystalline thermoplastic resin in which the main chain and side chains are composed of saturated bonds, olefin resins, polyacetal resins and the like can be mentioned, and one or two or more of them can be used in combination. Examples of the olefin-based resin (PO) include polyethylene-based resin (PE), polypropylene-based resin (PP), polybutene-based resin (PB), and the like. Among the olefin-based resins, polypropylene-based resins are particularly preferable from the viewpoint of heat resistance and moldability of the thermoplastic resin composition. block PP) or any.

In the dynamic cross-linking step of the present invention, a water component is added and kneaded. The water component may be blended directly into the kneader as a liquid, or a mixture containing the water component is prepared by mixing with fillers, water-absorbing polymers, etc., and the prepared mixture is blended. may Compounds containing water of crystallization (organic compounds, inorganic compounds, mixtures of organic and inorganic compounds, etc.), hydroxides, and other compounds that release a water component from the compounds by heating or the like may also be blended. These can be used singly or in combination of two or more. Since the water component evaporates when it is added to the heated kneader, it is preferable to add about 1 to 10 times the theoretical amount to convert the alkoxysilyl group to the silanol group. The blending amount of the water component is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer and/or rubber material.

In the dynamic cross-linking step, the alkoxysilyl groups of the thermoplastic elastomer and/or rubber material having the alkoxysilyl groups whose radical activity has been deactivated, which have formed the sea structure part of the sea-island structure, come into contact with the water component. As a result, a hydrolysis reaction occurs and the alkoxysilyl group changes to a silanol group. Then, the silanol groups undergo a condensation reaction (dehydration condensation reaction) to form a siloxane bond. A thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated by hydrolyzing the alkoxysilyl groups to convert them to silanol groups, further condensing the silanol groups, and forming siloxane bonds. becomes higher than the viscosity of the thermoplastic resin, and a phase transition occurs to the island structure portion. On the other hand, the thermoplastic resin that has formed the island structure portion of the sea-island structure undergoes a phase transition to the sea structure portion. In the dynamic cross-linking step, the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated undergoes a phase transition from the sea structure portion to the island structure portion, and the thermoplastic resin is transferred from the island structure portion to the sea structure. By phase transition to the structural part, the thermoplastic elastomer and/or rubber material having an alkoxysilyl group whose radical activity has been deactivated and the thermoplastic resin are phase-inverted to form the thermoplastic resin composition. obtain. FIG. 1 shows the reaction behavior until the alkoxysilyl groups form siloxane bonds via silanol groups in the case of a thermoplastic elastomer composed of saturated bonds having alkoxysilyl groups whose radical activity has been deactivated.

The thermoplastic resin composition is pelletized and made into automobile parts, waterproof materials, building materials, industrial members, etc. by known resin molding such as extrusion molding and injection molding.

The kneader 10 shown in FIG. 2 can continuously perform the grafting step, the reaction termination step, the kneading step, and the dynamic cross-linking step in one kneader. This kneader is suitable for the method for producing a thermoplastic resin composition. A single-screw extruder, a twin-screw extruder, a kneader, or the like can be used as the kneader. In particular, a twin-screw extruder is preferable from the viewpoint of reactive extrudability and self-cleaning properties.

The kneader 10 has a first zone in which the grafting step is performed, a second zone in which the reaction termination step is performed, a third zone in which the kneading step is performed, and the dynamic cross-linking process, from the upstream side to the downstream side. A screw provided inside the cylinder is rotated by a motor M, and the kneaded material is sequentially moved downstream (first zone → second zone → third zone → fourth zone). It is structured to send to
In the cylinder, a first supply port 11 is provided for the first zone in which the grafting step is performed, a second supply port 12 is provided in the second zone for the reaction termination step, and a third supply port is provided in the third zone for the kneading step. A fourth supply port 14 is provided in the port 13 and the fourth zone where the dynamic cross-linking process is performed.

The production of a thermoplastic resin composition using the kneader 10 will be described. From the first supply port 11, the thermoplastic elastomer and/or rubber material, the silane coupling agent, the reaction initiator, the silanol cross-linking acceleration catalyst that is appropriately blended, and appropriate additives are introduced into the cylinder. and melt-kneaded in the first zone where the grafting step is performed. By kneading in the first zone, the thermoplastic elastomer and/or rubber material is grafted with alkoxysilyl groups to produce the thermoplastic elastomer and/or rubber material having the alkoxysilyl groups, and then transferred to the second zone. send.

In the second zone where the reaction termination step is performed, the reaction termination agent is supplied into the cylinder from the second supply port 12, melted and kneaded, and the kneaded material is sent to the next third zone. The timing of supplying the reaction terminator from the second supply port 12 into the kneader 10 is after the grafting step (before the kneading step). In the reaction terminating step, the reaction terminator deactivates free radicals derived from the reaction initiator blended for grafting the alkoxysilyl group to the thermoplastic elastomer and/or rubber material.

In the third zone where the kneading step is performed, the thermoplastic resin and appropriate additives are supplied into the cylinder from the third supply port 13, melted and kneaded, and the kneaded product is sent to the next fourth zone.

In the fourth zone where the dynamic cross-linking step is performed, the water component is supplied into the cylinder through the fourth supply port 14 and melt-kneaded. In the kneading in the fourth zone, the alkoxysilyl groups of the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated are converted to silanol groups by hydrolysis reaction with the water component, and then the silanol groups are formed. They are dehydrated and condensed to form a siloxane bond. The thermoplastic elastomer having the alkoxysilyl group whose radical activity has been deactivated and/or the thermoplastic elastomer having the alkoxysilyl group whose radical activity has been deactivated by converting the alkoxysilyl group of the rubber material into a siloxane bond and/or Alternatively, the thermoplastic elastomer and/or rubber having the alkoxysilyl group whose radical activity has been deactivated until the viscosity of the rubber material becomes higher than that of the thermoplastic resin, and the sea structure part of the sea-island structure has been formed. The material phase transitions to the island structure portion, and the thermoplastic resin, which had formed the island structure portion of the sea-island structure, to the sea structure portion, and the alkoxysilyl group whose radical activity has been deactivated is transferred to the sea structure portion. The thermoplastic resin composition is obtained by inverting the thermoplastic elastomer and/or rubber material and the thermoplastic resin. The thermoplastic resin composition extruded from the kneader 10 is then pelletized by a pelletizer and used for resin molding such as extrusion molding and injection molding.

The grafting step is performed in advance, and the obtained thermoplastic elastomer and/or rubber material having an alkoxysilyl group in which the radical activity is deactivated is stored, and at a later date, the stored radical activity is A thermoplastic resin composition having the sea-island structure may be produced through the kneading step and the dynamic cross-linking step using a thermoplastic elastomer and/or a rubber material having an alkoxysilyl group inactivated by .

Using the following raw materials, thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 having the formulation shown in FIG. 3 were produced with a kneader. The numbers for each component in the formulation of FIG. 3 are parts by weight. Also, for Comparative Examples 1 and 2, product name: Santoprene 201-64: manufactured by Exxon Mobil Corporation was used. As a kneader, the kneader 10 described above comprising a twin-screw extruder (L/D=72) having zones 1 to 4 was used.

The manufacturing conditions using the kneader 10 are as follows: first zone temperature: 230°C, second to fourth zone temperatures: 200°C, screw rotation speed: 400 rpm, discharge rate at outlet: 30 kg/hr. rice field.
The temperature of the first zone is appropriately set according to the melting point of the raw material used (thermoplastic elastomer, rubber material, etc.) and the decomposition temperature of the reaction initiator used. is preferred. The temperatures of the second to fourth zones are preferably set 10 to 30° C. higher than the melting point of the raw material (thermoplastic resin, etc.) used. As a guideline for the temperature range, it is 180 to 230° C. when the thermoplastic resin is a polypropylene-based resin or a polystyrene-based resin.

・TPE (olefin-based): ethylene/1-octene copolymer, manufactured by Dow Chemical Company, product name: ENGAGE 8842
・Rubber: Ethylene propylene diene rubber (EPDM), manufactured by Dow Chemical Japan, product name: NORDEL IP 4760P
· Cross-linking agent (silane coupling agent): vinyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-1003
・Reaction initiator: Aliphatic organic peroxide, manufactured by NOF Corporation, product name: Perhexa 25B, generates two radicals from one molecule.
· Reaction terminator-1: Hindered phenol-based antioxidant, manufactured by ADEKA, product name: Adekastab AO-80, one molecule captures two free radicals.
· Reaction terminator-2: Hindered phenolic antioxidant, product name: ADEKA STAB AO-20, one molecule captures three free radicals.
· Reaction terminator-3: Hindered phenol-based antioxidant, manufactured by ADEKA, product name: Adekastab AO-60, one molecule captures four free radicals.
・Silanol cross-linking accelerator catalyst: octyl tin compound, manufactured by ADEKA, product name: ADEKA STAB OT-1
・ TP: polypropylene resin (block type), manufactured by Japan Polypropylene Corporation, product name: Novatec EC7
・ Coloring agent: Color masterbatch, manufactured by Tokyo Ink Co., Ltd., product name: PEX3162 BLUE

Examples 1 and 2 are examples in which the grafting step, the reaction termination step, the kneading step, and the dynamic cross-linking step were performed continuously, and the amount of reaction terminator-1 (reaction termination for the reaction initiator This is an example in which the ratio of Agent-1) is changed. In both Examples 1 and 2, TPE was blended, and rubber and colorant were not blended. In Example 1, the amount of reaction terminator-1 was 0.26 parts by weight, the ratio of reaction terminator-1 to the reaction initiator (proportion of the number of moles) was 102%, and Example 2 was the reaction terminator. The amount of terminator-1 was 0.50 parts by weight, and the ratio of reaction terminator-1 to the reaction initiator (percentage of moles) was 196%.

Example 3 is an example in which rubber is blended in place of TPE in Example 1, and the rest is the same as Example 1.
Example 4 is an example in which a coloring agent is added to Example 1, and the rest is the same as Example 1.
In Example 5, 0.22 parts by weight of reaction terminator-2 was blended in place of reaction terminator-1 in Example 1, and the ratio (molar ratio) of reaction terminator-2 to the reaction initiator was 122. %, and the rest is the same as in Example 1.
In Example 6, 0.30 parts by weight of reaction terminator-3 was blended in place of reaction terminator-1 in Example 1, and the ratio (molar ratio) of reaction terminator-3 to the reaction initiator was 148. %, and the rest is the same as in Example 1.

Comparative Example 1 is an example of phenol cross-linking (complete cross-linking), Comparative Example 2 is an example in which a coloring agent is blended in Comparative Example 1, Comparative Example 3 is an example in which the reaction terminator-1 of Example 1 is 0 parts by weight, and comparison Example 4 is an example in which 0.23 parts by weight of the reaction terminator-1 of Example 1 was used, and the ratio of the reaction terminator-1 to the reaction initiator (molar ratio) was 90%.

For each example and each comparative example, the phase transition, the sea-island structure, the maximum value (theoretical value) (parts by weight) of the gel component (insoluble matter) of the island structure portion, and the amount of the gel component (insoluble matter) of the island structure portion Measured value (parts by weight), island structure gel fraction (%), tensile strength (MPa), compression set (%), color difference value due to weather deterioration (ΔE*ab), color difference value due to coloring (ΔE*ab ), and examined for remeltability. Results are shown in FIG. Note that the color difference value (ΔE*ab) due to weather resistance deterioration has not been measured for Example 3.

The presence or absence of phase transition and the presence or absence of a sea-island structure were confirmed by preparing a thin film with an ultramicrotome (FC6: manufactured by Leica) and observing it with a transmission electron microscope (H-7650: manufactured by Hitachi High-Technologies Corporation).
The maximum value of the gel component (insoluble matter) of the island structure portion is the compounding amount of TPE and/or rubber (100 parts by weight).
The measured value of the gel fraction of the island structure portion conforms to JIS K6769:2004.

The gel fraction (%) of the island structure portion was calculated by [(the measured value of the gel fraction of the island structure portion/the maximum value of the gel fraction of the island structure portion)×100].
Tensile strength (MPa) was measured according to JIS K6251:2010 (dumbbell shape No. 3×thickness 2 mm).
The compression set (%) was measured in accordance with JIS K6262:2013 A method (small-diameter test piece (three laminated pieces of diameter 13 mm x thickness 2 mm) 70°C x 22 hours, 25% compression).

The color difference value (ΔE*ab) due to weather resistance deterioration is measured by a color difference meter (SM color computer SM-T: manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS Z8781-4:2013. ) is the color difference of the thermoplastic resin composition before and after weathering deterioration. In addition, the weather resistance deterioration test was performed in accordance with JIS K7350-2: 2008 B method, using a light resistance tester (SC-700FP: manufactured by Suga Test Instruments Co., Ltd.) with a xenon lamp with an irradiance of 150 W / m ² (wavelength range from 300 to 400 nm), cumulative irradiation dose: 300 MJ/m ² , black panel temperature: 63±3°C.

The color difference value due to coloring was measured in accordance with JIS Z8781-4:2013 in the same manner as the above color difference value due to weather deterioration with respect to the colorability (color development) depending on the presence or absence of the coloring agent. The color difference value (ΔE*ab) due to coloring is the color difference value of the thermoplastic resin composition due to the addition of the colorant, and was measured for Example 4 and Comparative Example 2 in which the colorant was added. The color difference value due to coloring in Example 4 was measured against Example 1 (coloring agent not mixed), and the color difference value due to coloring in Comparative Example 2 was measured against Comparative Example 1 (coloring agent not mixed). rice field. A larger value of ΔE*ab indicates better colorability.

Color difference value: ΔE*ab is defined as the Euclidean distance between coordinates in CIE 1976 L*a*b* color space and indicates the color difference between two color stimuli calculated by the following formula.
ΔE*ab=[(ΔL*) ² +(Δa*) ² +(Δb*) ² )] ^1/2
Also, the color difference value: ΔE*ab can be expressed in the NBS unit and the sense of color difference (sensory evaluation of the degree of color difference) defined by the US National Bureau of Standards, as shown in FIG. The numerical values in the column of NBS units in FIG. 4 are the values of ΔE*ab calculated by the above formula.

For remeltability, each example and each comparative example was hot-pressed at 180° C. for 3 minutes, and the presence or absence of melting was confirmed. A case of melting was evaluated as "O", and a case of not melting was evaluated as "X".

In Examples 1 to 6, the phase transition is “yes” and the sea-island structure is “yes”, and the gel fraction of the island structure portion is 96 to 98%. Further, Examples 1 to 6 had a tensile strength of 10.6 to 13.3 MPa, a compression set of 26 to 30%, good mechanical properties, and a remeltability of "○". When used for automobile parts, water stop materials, building materials, industrial members, etc., the tensile strength is preferably 7 MPa or more, more preferably 10 MPa or more, and the compression set is preferably 50% or less, more preferably 50% or less. 40% or less. In Examples 1 to 6, the gel fraction of the island structure portion was 96 to 98%, and the compression set was as low as 26 to 30% because the silane coupling agent was used for complete cross-linking. Since the free radicals generated by the reaction initiator have their radical activity deactivated by the reaction terminator, the tensile strength is 10.6 to 13.3 MPa, which is sufficiently high mechanical strength. It can be suitably used as building materials, industrial members, and the like.

Comparing Example 1 and Example 4 with respect to colorability, the color difference value (Δ*abE) due to coloration when 0.01 part by weight of the colorant was blended with 100 parts by weight of TPE was 5. , the NBS unit was in the range of 3.0 to 6.0, the color difference was at a noticeable level, and the coloring property was excellent.

Examples 1 to 2 and Examples 4 to 6 using a thermoplastic elastomer whose main chain and side chains are saturated bonds and a thermoplastic resin whose main chain and side chains are saturated bonds are color difference values (ΔE *ab) is 2.4 to 2.6, and the color difference value due to weather deterioration is small.

Comparative Example 1 is an example of phenol cross-linking of rubber (EPDM) having double bonds in side chains, phase transition “yes”, sea-island structure “yes”, and gel fraction of island structure portion is 99%. , the tensile strength was 6.4 MPa, the compression set was 33%, and the remeltability was "◯".
Comparative Example 1 has a low tensile strength, and since the rubber is phenol-crosslinked, the color difference value due to weather deterioration (ΔE*ab) is 13.2, which is a large color difference value due to weather resistance deterioration.

Comparative Example 2 is an example in which a coloring agent is added to Comparative Example 1, and the phase transition is “yes”, the sea-island structure is “yes”, the gel fraction of the island structure portion is 99%, and the tensile strength is 6. 0.5 MPa, the compression set was 35%, and the remeltability was "◯". Comparing Comparative Example 1 and Comparative Example 2, the color difference value (ΔE*ab) due to coloring when 0.01 part by weight of the coloring agent was blended with 100 parts by weight of Santoprene 201-64 was 0.8. The NBS unit is located between 0.5 and 1.5, and the sense of color difference is at a level that is slightly felt, and is inferior to the color difference value (ΔE*ab) 5 due to coloring in Example 4. Met. This indicates that the phenol itself used for phenol crosslinking has a color tone, and even if a coloring agent is added, the coloring property is low. The color difference value (ΔE*ab) due to the coloring of the phenol crosslinked thermoplastic resin composition can be increased by increasing the amount of the coloring agent, but it becomes difficult to obtain a light color. In particular, in the CIE1976L*a*b* color space, it is very difficult to give a phenolic crosslinked thermoplastic resin composition a light color that is opposite to the color tone of the phenolic crosslinking agent itself. This indicates that the thermoplastic resin composition of the present invention can be colored lightly, which is difficult to do with a phenol-crosslinked thermoplastic resin composition, and has excellent coloring flexibility.
In Comparative Example 2, the tensile strength is low, and since the rubber is phenol-crosslinked, the color difference value (ΔE*ab) due to weather deterioration is 14.2, which is large.

Comparative Example 3 is an example in which the reaction terminator-1 in Example 1 is not blended, the phase transition is “yes”, the sea-island structure is “yes”, the gel fraction of the island structure portion is 98%, and the tensile strength is The compression set was 4.1 MPa, the compression set was 52%, the color difference value (ΔE*ab) due to weather deterioration was 2.7, and the remeltability was "good". Comparative Example 3 is significantly inferior to Example 1 in terms of tensile strength and mechanical strength of compression set because reaction terminator-1 of Example 1 is not blended.

Comparative Example 4 is an example in which the compounding amount of the reaction terminator-1 in Example 1 was 0.23 parts by weight, and the ratio of the reaction terminator-1 to the reaction initiator (proportion of the number of moles) was 90%. Phase transition “yes”, sea-island structure “yes”, gel fraction of island structure part is 98%, tensile strength is 6.8 MPa, compression set is 43%, color difference value due to weather deterioration (ΔE*ab) was 2.7, and the remeltability was "O". Comparative Example 4 is slightly improved in tensile strength and compression set compared to Comparative Example 1 in which reaction terminator-1 is not blended. However, in Comparative Example 4, the amount of reaction terminator-1 compounded was smaller than that in Example 1, and the ratio of reaction terminator-1 to the reaction initiator (percentage of moles) was as low as 90%. Compared to , the mechanical strength of tensile strength and compression set is greatly inferior.

Thus, the thermoplastic resin composition obtained by the present invention is excellent in colorability and mechanical properties, and can be remolded by remelting. preferred. Furthermore, by using a thermoplastic elastomer in which the main chain and side chains are composed of saturated bonds, it is possible to prevent deterioration in weather resistance.

The present invention has excellent mechanical properties and colorability in applications that require weather resistance, such as automobile parts, water stop materials, building materials, and industrial materials. The purpose is to provide a thermoplastic resin composition that is unlikely to occur, and it can be said that it has the following characteristics as a technical means for solving the object.
<Feature 1>
A thermoplastic resin composition having a sea-island structure,
the sea structure part of the sea-island structure is composed of a thermoplastic resin in which the main chain and side chains are composed of saturated bonds,
The island structure part of the sea-island structure is composed of a thermoplastic elastomer in which the main chain and side chains crosslinked by siloxane bonds are composed of saturated bonds,
The gel fraction (in accordance with JIS K6769:2004) of the island structure portion is 90% or more,
The free radicals generated by the reaction initiator contained in the thermoplastic resin composition are radically activated by the reaction terminator contained in the thermoplastic resin composition at a rate of 100% or more with respect to the reaction initiator. A thermoplastic resin composition characterized in that it has been deactivated.
<Feature 2>
A thermoplastic elastomer composed of saturated bonds having alkoxysilyl groups, which is obtained by grafting alkoxysilyl groups to a thermoplastic elastomer composed of saturated bonds in the main chain and side chains, and a reaction terminator are brought into a molten state in a kneader. An alkoxysilyl whose radical activity has been deactivated by deactivating free radicals derived from a reaction initiator that is kneaded and blended to produce a thermoplastic elastomer composed of saturated bonds having alkoxysilyl groups with the reaction terminator. a reaction termination step of producing a thermoplastic elastomer composed of saturated bonds having groups;
a kneading step of kneading the thermoplastic elastomer composed of saturated bonds having alkoxysilyl groups whose radical activity has been deactivated and the thermoplastic resin composed of saturated bonds in the main chain and side chains in a kneader in a molten state;
A water component is added to the kneader, and the alkoxysilyl groups of the thermoplastic elastomer composed of saturated bonds having alkoxysilyl groups whose radical activity has been deactivated are hydrolyzed in the kneader with the water component to produce silanol. a dynamic cross-linking step of grouping and then condensing the silanol groups to form a siloxane bond;
has
The reaction terminator added in the reaction termination step has a mole ratio of 100% or more with respect to the mole number of the reaction initiator,
A method for producing a thermoplastic resin composition, wherein the thermoplastic resin composition obtained by the dynamic crosslinking step has a sea-island structure.

A first aspect of the invention is a thermoplastic resin composition having a sea-island structure, wherein the sea structure portion of the sea-island structure is made of a thermoplastic resin, and the island structure portion of the sea-island structure is crosslinked by siloxane bonding. A reaction initiator contained in the thermoplastic resin composition, which is composed of a thermoplastic elastomer and/or a rubber material and has a gel fraction (in accordance with JIS K6769:2004) of 90% or more in the island structure portion. The free radicals generated by the reaction are deactivated by the reaction terminator contained in the thermoplastic resin composition at a molar ratio of 100% or more with respect to the molar number of the reaction initiator.

A second aspect of the invention is the aspect of the first invention, wherein the thermoplastic elastomer and/or the rubber material is a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds, and the thermoplastic resin is mainly It is characterized by being a thermoplastic resin in which the chains and side chains are composed of saturated bonds.

A third aspect of the invention is the first or second aspect of the invention , wherein the thermoplastic resin composition is a building material joint material or building material water stop material, a vehicle interior material, a vehicle exterior material, an It is characterized by being used as a hose material.

In a fourth aspect of the invention , a thermoplastic elastomer and/or rubber material having an alkoxysilyl group, in which an alkoxysilyl group is grafted to a thermoplastic elastomer and/or rubber material, and a reaction terminator are mixed in a kneader. is kneaded to a molten state, and the free radicals derived from the reaction initiator blended for producing the thermoplastic elastomer and / or rubber material having the alkoxysilyl group are deactivated by the reaction terminator, and the radical activity is A reaction stopping step of producing a thermoplastic elastomer and/or rubber material having deactivated alkoxysilyl groups, a thermoplastic elastomer and/or rubber material having the alkoxysilyl groups whose radical activity has been deactivated, and a thermoplastic resin. are kneaded into a molten state in a kneader, a water component is added to the kneader, and the thermoplastic elastomer and / or rubber material having an alkoxysilyl group whose radical activity is deactivated in the kneader. The alkoxysilyl group of and the water component are hydrolyzed to form a silanol group, and then the silanol groups are subjected to a condensation reaction to form a siloxane bond, and the reaction termination step The ratio of the number of moles of the reaction terminator to be added in step is 100% or more with respect to the number of moles of the reaction initiator, and the thermoplastic resin composition obtained by the dynamic crosslinking step has a sea-island structure. It relates to a method for producing a thermoplastic resin composition.

A fifth aspect of the invention is based on the fourth aspect of the invention, wherein in the dynamic crosslinking step, the alkoxysilyl groups of the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated are the When the siloxane bond is formed via the silanol group, the viscosity of the thermoplastic elastomer and/or rubber material having the alkoxysilyl group whose radical activity is deactivated becomes higher than the viscosity of the thermoplastic resin, and the The thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity is deactivated undergoes a phase transition to the island structure portion of the sea-island structure, and the thermoplastic resin undergoes a phase transition to the sea structure portion of the sea-island structure. characterized by

A sixth aspect of the invention is the fourth or fifth aspect of the invention , characterized in that the gel fraction (in accordance with JIS K6769:2004) of the island structure portion of the sea-island structure is 90% or more. .

A seventh aspect of the invention is, in any one of the fourth to sixth aspects of the invention , the thermoplastic elastomer and/or Grafting in which a rubber material, a silane coupling agent, and a reaction initiator are added and kneaded in the kneader in a molten state to graft the silane coupling agent to the thermoplastic elastomer and/or rubber material. and the grafting step, the reaction termination step, the kneading step, and the dynamic cross-linking step are continuously performed in the kneader.

An eighth aspect of the invention is characterized in that, in any one of the fourth to seventh aspects of the invention , the sea structure portion of the sea-island structure is made of the thermoplastic resin and is remeltable. .

A ninth aspect of the invention is that in any one of the fourth to eighth aspects of the invention , 0.01 part by weight of a colorant is blended with 100 parts by weight of the thermoplastic elastomer and/or the rubber material. A color difference value of ΔE*ab (based on JIS Z8781-4:2013) due to coloring of the thermoplastic resin composition is 1.5 or more.

A tenth aspect of the invention is characterized in that, in any one of the fourth to ninth aspects of the invention , the thermoplastic resin is a crystalline thermoplastic resin.

According to an eleventh aspect of the invention, in any one of the fourth to tenth aspects of the invention , the thermoplastic elastomer and/or the rubber material is a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds, The thermoplastic resin is characterized in that the main chain and side chains are thermoplastic resins composed of saturated bonds.

A twelfth aspect of the invention is characterized in that, in the eleventh aspect of the invention , the thermoplastic resin in which the main chain and the side chains are composed of saturated bonds is an olefin resin.

A thirteenth aspect of the invention is characterized in that, in the twelfth aspect of the invention , the olefin-based resin is a polypropylene-based resin.

A fourteenth aspect of the invention is characterized in that, in the twelfth or thirteenth aspect of the invention , the thermoplastic elastomer in which the main chain and side chains are composed of saturated bonds is a polyethylene/α-olefin copolymer. .

A fifteenth aspect of the invention is that in any one of the twelfth to fourteenth aspects of the invention , the color difference value after weathering deterioration of the thermoplastic resin composition: ΔE*ab (JIS Z8781-4:2013 compliant) is , 0 to 3.

A sixteenth aspect of the invention is that in any one of the fourth to fifteenth aspects of the invention, the thermoplastic resin composition is It is characterized by being used as a material and industrial hose material.

According to the first and third aspects of the invention , the thermoplastic elastomer and/or rubber material in which the sea structure part of the sea-island structure is made of a thermoplastic resin, and the island structure part of the sea-island structure is crosslinked by siloxane bonds. The gel fraction (JIS K6769: 2004 compliant) of the island structure portion is 90% or more, and the free radicals generated by the reaction initiator contained in the thermoplastic resin composition are Since the radical activity is deactivated, the thermoplastic resin composition has good mechanical properties and colorability, can be re-melted and re-molded, has little deterioration in physical properties, and has a high degree of freedom in molding. is obtained.

According to the aspects of the second to third inventions , a thermoplastic elastomer having a main chain and side chains composed of saturated bonds and a thermoplastic resin having a main chain and side chains composed of saturated bonds are used as raw materials, and a silane coupling agent Because dynamic crosslinking is performed using , the thermoplastic resin composition has excellent mechanical properties and colorability, can be remelted and remolded, and has a high degree of freedom in molding, and is resistant to weather deterioration. you get something.

According to the fourth to sixteenth aspects of the invention , dynamic crosslinking is performed using a silane coupling agent, and free radicals generated by the reaction initiator have their radical activity deactivated by the reaction terminator. Therefore, it is possible to obtain a thermoplastic resin composition that has good mechanical properties and colorability, can be remelted and remolded, and has a high degree of freedom in molding.

According to the twelfth to sixteenth aspects of the invention , a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds and a thermoplastic resin whose main chain and side chains are composed of saturated bonds are used as raw materials, and a silane coupling agent Because dynamic crosslinking is performed using , the thermoplastic resin composition has excellent mechanical properties and colorability, can be remelted and remolded, and has a high degree of freedom in molding, and is resistant to weather deterioration. you get something.

Claims (16)

A thermoplastic resin composition having a sea-island structure,
the sea structure part of the sea-island structure is made of a thermoplastic resin,
The island structure part of the sea-island structure is composed of a thermoplastic elastomer and/or a rubber material crosslinked by siloxane bonds,
The gel fraction (in accordance with JIS K6769:2004) of the island structure portion is 90% or more,
A reaction in which the free radicals generated by the reaction initiator contained in the thermoplastic resin composition are contained in the thermoplastic resin composition at a molar ratio of 100% or more with respect to the mole number of the reaction initiator. A thermoplastic resin composition, wherein the radical activity is deactivated by a terminating agent. The thermoplastic elastomer and/or rubber material is a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds,
2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a thermoplastic resin in which the main chain and side chains are composed of saturated bonds. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition is used as a joint material for building materials, a water stop material for building materials, an interior material for vehicles, an exterior material for vehicles, and an industrial hose material. A plastic resin composition. A thermoplastic elastomer and/or rubber material having an alkoxysilyl group grafted onto a thermoplastic elastomer and/or rubber material and a reaction terminator are kneaded in a kneader in a molten state, and Free radicals derived from a reaction initiator blended for producing a thermoplastic elastomer and/or rubber material having alkoxysilyl groups are deactivated by the reaction terminator, and have alkoxysilyl groups whose radical activity has been deactivated. a step of quenching the thermoplastic elastomer and/or rubber material;
a kneading step of kneading the thermoplastic elastomer and/or rubber material having an alkoxysilyl group whose radical activity is deactivated and a thermoplastic resin in a kneader in a molten state;
A water component is added to the kneader, and the alkoxysilyl group of the thermoplastic elastomer and/or rubber material having the alkoxysilyl group whose radical activity is deactivated is hydrolyzed in the kneader with the water component. A dynamic cross-linking step of forming silanol groups and then condensing the silanol groups to form siloxane bonds;
has
The reaction terminator added in the reaction termination step has a mole ratio of 100% or more with respect to the mole number of the reaction initiator,
A method for producing a thermoplastic resin composition, wherein the thermoplastic resin composition obtained by the dynamic crosslinking step has a sea-island structure. In the dynamic cross-linking step,
When the alkoxysilyl groups of the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated form the siloxane bonds via the silanol groups,
The viscosity of the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated becomes higher than the viscosity of the thermoplastic resin,
the thermoplastic elastomer and/or rubber material having alkoxysilyl groups whose radical activity has been deactivated undergoes a phase transition to the island structure portion of the sea-island structure;
5. The method for producing a thermoplastic resin composition according to claim 4, wherein the thermoplastic resin undergoes a phase transition to the sea structure portion of the sea-island structure. 6. The method for producing a thermoplastic resin composition according to claim 4, wherein the island structure part of the sea-island structure has a gel fraction (JIS K6769:2004 compliant) of 90% or more. In order to produce the thermoplastic elastomer and/or rubber material having the alkoxysilyl group,
The thermoplastic elastomer and/or rubber material, a silane coupling agent, and a reaction initiator are added and kneaded in a molten state in the kneader, thereby adding the silane cup to the thermoplastic elastomer and/or rubber material. Having a grafting step of grafting the ring agent,
7. The grafting step, the reaction terminating step, the kneading step, and the dynamic cross-linking step are carried out continuously in the kneader according to any one of claims 4 to 6. A method for producing the thermoplastic resin composition according to the item. 8. The method for producing a thermoplastic resin composition according to any one of claims 4 to 7, wherein the sea structure part of the sea-island structure is made of the thermoplastic resin and is remeltable. Color difference value due to coloring of the thermoplastic resin composition when 0.01 part by weight of the colorant is blended with 100 parts by weight of the thermoplastic elastomer and/or rubber material in which the radicals are deactivated: ΔE*ab (JIS Z8781-4:2013) is 1.5 or more, the method for producing a thermoplastic resin composition according to any one of claims 4 to 8. 10. The method for producing a thermoplastic resin composition according to any one of claims 4 to 9, wherein the thermoplastic resin is a crystalline thermoplastic resin. The thermoplastic elastomer and/or rubber material is a thermoplastic elastomer whose main chain and side chains are composed of saturated bonds,
11. The method for producing a thermoplastic resin composition according to any one of claims 4 to 10, wherein the thermoplastic resin is a thermoplastic resin whose main chain and side chains are composed of saturated bonds. 12. The method for producing a thermoplastic resin composition according to claim 11, wherein the thermoplastic resin in which the main chain and side chains are composed of saturated bonds is an olefin resin. 13. The method for producing a thermoplastic resin composition according to claim 12, wherein the olefin resin is a polypropylene resin. 14. The thermoplastic resin composition according to any one of claims 12 and 13, wherein the thermoplastic elastomer in which the main chain and side chains are composed of saturated bonds is a polyethylene/α-olefin copolymer. Production method. The color difference value after weathering deterioration of the thermoplastic resin composition: ΔE*ab (JIS Z8781-4:2013) is 0 to 3. The heat according to any one of claims 12 to 14. A method for producing a plastic resin composition. 16. The thermoplastic resin composition according to any one of claims 4 to 15, wherein the thermoplastic resin composition is used as a joint material for building materials, a water stop material for building materials, an interior material for vehicles, an exterior material for vehicles, and an industrial hose material. A method for producing the thermoplastic resin composition according to the item.

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